It is often assumed that recollection is necessary to support memory for novel associations, whereas familiarity supports memory for single items. However, the levels of unitization framework assumes that familiarity can support associative memory under conditions in which the components of an association are unitized (i.e., treated as a single coherent item). In the current study we tested two critical assumptions of this framework. First, does unitization reflect a specialized form of learning or is it simply a form of semantic or elaborative encoding, and, second, can the beneficial effects of unitization on familiarity be observed for across-domain associations or are they limited to creating new associations between items that are from the same stimulus domains? Unitization was found to increase associative recognition but not item recognition. It affected familiarity more than recollection, increased associative but not item priming, and was dissociable from levels of processing effects. Moreover, unitization effects were found to be particularly effective in supporting face-word and fractal-sound pairs. The current results indicate that unitization reflects a specialized form of learning that supports associative familiarity of within- and across-domain associations.